CN108148184B - 一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物及其制备方法和应用 - Google Patents

一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物及其制备方法和应用 Download PDF

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CN108148184B
CN108148184B CN201711313929.XA CN201711313929A CN108148184B CN 108148184 B CN108148184 B CN 108148184B CN 201711313929 A CN201711313929 A CN 201711313929A CN 108148184 B CN108148184 B CN 108148184B
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quinoxaline
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acenaphtho
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兰柳元
麦裕良
文武
李岱远
张磊
高敏
廖兵
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Abstract

本发明公开了一种含苊并[1,2‑b]喹喔啉二酰亚胺的共轭聚合物及其制备方法和应用，该含苊并[1,2‑b]喹喔啉二酰亚胺的共轭聚合物的结构通式为：
Figure DDA0001503436690000011
其中，R1和R2独立地选自‑H、C1～C24的烷基或C1～C24的烷氧基，Ar为芳香基团，n为1～10000的自然数，0＜x＜1，0＜y＜1，x+y＝1。其制备方法如下：1)单体N‑R1‑N′‑R2‑7,10‑二(5‑溴‑噻吩‑2‑基)‑1H‑吡啶并[3',4',5',5,6]苊并[1,2‑b]喹喔啉‑8,9‑二元羧酸酰亚胺‑1,3(2H)‑二酮的制备；2)金属催化偶联反应。本发明的含苊并[1,2‑b]喹喔啉二酰亚胺的共轭聚合物结构新颖，热稳定性好，太阳光子吸收能力强，电子能级合适，适合用于有机太阳能电池中的电子受体或电子给体材料，且其可溶于氯仿、四氢呋喃、氯苯等有机溶剂，可采用溶液法加工。

Description

一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物及其制备 方法和应用
技术领域
本发明涉及一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物及其制备方法和应用。
背景技术
有机太阳能电池具有成本低、重量轻、半透明、可通过溶液加工成大面积的柔性薄膜器件等优点，受到广泛的关注。近年来，随着活性层材料、器件结构和制备工艺条件的不断优化，有机太阳能电池发展迅速，成果显著。目前，通过聚合物给体或小分子给体与富勒烯受体共混制备的太阳能电池的光电转化效率已突破11％，市场化前景一片光明。要想获得高效的有机太阳能电池器件，材料是最重要的决定因素之一。
目前，给体材料发展迅速，而受体材料则发展缓慢。受体材料方面，由于PCBM具有电子亲和力强、电子迁移率高等优点，且能够与共轭聚合物给体材料混合形成纳米尺寸的相分离结构，使得以PC61BM和PC71BM为代表的富勒烯衍生物占据着主导地位。然而，以PCBM为代表的富勒烯衍生物自身也存在着难以克服的缺点，例如：在可见光区吸收弱，能级难于调控，导致开路电压较低，限制了光电转换效率的进一步提高。相比之下，非富勒烯类聚合物受体材料的结构易于修饰，能级容易进行微调，其与给体材料的能级能够很好地相互匹配，从而可以获得高的开路电压。近几年，人们为了替换有机太阳能电池中的富勒烯受体，合成了一系列新型聚合物受体材料，当他们与不同的给体材料共混制备太阳能电池时，表现出了良好的光电性能。然而，目前聚合物受体材料的开发尚显不足，局限于苝二酰亚胺、萘二酰亚胺和B-N化合物材料。因此，为了实现有机太阳能电池高效的光电转换，加速其商业化进程，从活性层材料的角度考虑，合成更多性能优异的新型聚合物受体材料就显得十分重要。
发明内容
本发明的目的在于提供一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物及其制备方法和应用。
本发明所采取的技术方案是：
一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物，结构通式为：
Figure BDA0001503436670000021
其中，R1和R2独立地选自-H、C1～C24的烷基或C1～C24的烷氧基，Ar为芳香基团，n为1～10000的自然数，0＜x＜1，0＜y＜1，x+y＝1。
所述的芳香基团为如下所示结构中的至少一种：
Figure BDA0001503436670000022
其中，R、Ra、Rb、Rc和Rd独立地选自-H、烷基、不饱和烷基、卤代烷基、烷氧基、羧基取代烷基、氨基取代烷基、氰基取代烷基、硝基取代烷基、羰基取代烷基或酯基。
上述含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物的制备方法，包括以下步骤：
1)以4,7-二(噻吩-2-基)-1,2,5-苯并噻二唑-N-R1基-5,6-二元羧酸酰亚胺为母体，加入铁粉进行还原，得到4,7-二(噻吩-2-基)-5,6-二氨基-N-R1基-异吲哚-1,3-二酮，再与2-R2-6,7-二氢-1H-茚并(6,7,1-def)异喹啉-1,3,6,7(2H)-四酮进行脱水缩合反应，得到N-R1-N′-R2-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮，再通过N-溴代琥珀酰亚胺溴化，得到单体N-R1-N′-R2-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮；
2)金属催化偶联反应：将含Ar结构的单体与步骤1)制备的单体反应，得到含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物。
本发明的有益效果是：本发明的含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物结构新颖，热稳定性好，太阳光子吸收能力强，电子能级合适，适合用于有机太阳能电池中的电子受体或电子给体材料，且其可溶于氯仿、四氢呋喃、氯苯等有机溶剂，可采用溶液法加工。
附图说明
图1为实施例4的含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物P1的紫外-可见吸收光谱。
图2为实施例4的含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物P1的热失重曲线。
具体实施方式
一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物，结构通式为：
Figure BDA0001503436670000031
其中，R1和R2独立地选自-H、C1～C24的烷基或C1～C24的烷氧基，Ar为芳香基团，n为1～10000的自然数，0＜x＜1，0＜y＜1，x+y＝1。
优选的，所述的芳香基团为如下所示结构中的至少一种：
Figure BDA0001503436670000041
其中，其中，R、Ra、Rb、Rc和Rd独立地选自-H、烷基、不饱和烷基、卤代烷基、烷氧基、羧基取代烷基、氨基取代烷基、氰基取代烷基、硝基取代烷基、羰基取代烷基或酯基。
优选的，所述的R、Ra、Rb、Rc和Rd独立地为C1～C24的烷基。
上述含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物的制备方法，包括以下步骤：
1)以4,7-二(噻吩-2-基)-1,2,5-苯并噻二唑-N-R1基-5,6-二元羧酸酰亚胺为母体，加入铁粉进行还原，得到4,7-二(噻吩-2-基)-5,6-二氨基-N-R1基-异吲哚-1,3-二酮，再与2-R2-6,7-二氢-1H-茚并(6,7,1-def)异喹啉-1,3,6,7(2H)-四酮进行脱水缩合反应，得到N-R1-N′-R2-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮，再通过N-溴代琥珀酰亚胺溴化，得到单体N-R1-N′-R2-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮；
2)金属催化偶联反应：将含Ar结构的单体与步骤1)制备的单体反应，得到含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物。
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1：
4,7-二(噻吩-2-基)-5,6-二氨基-N-R1基-异吲哚-1,3-二酮的制备，反应式如式I所示：
Figure BDA0001503436670000051
式I中的4,7-二(噻吩-2-基)-1,2,5-苯并噻二唑-N-R1基-5,6-二元羧酸酰亚胺(a)的合成参照文献[Wang LX,Cai DD,Zheng QD,et al.ACS Macro Lett.2013,2,605-608]。
以制备4,7-二(噻吩-2-基)-5,6-二氨基-N-(2-癸基十四烷基)-异吲哚-1,3-二酮为例予以说明：在50mL两口瓶中加入4,7-二(噻吩-2-基)-1,2,5-苯并噻二唑-N-(2-癸基十四烷基)-5,6-二元羧酸酰亚胺(1.41g，2mmol)和铁粉(1.34g，24mmol)，再加入30mL冰乙酸，氮气条件下搅拌回流5h，再将反应液倒入水中，析出黄绿色固体，过滤，取滤渣，用硅胶层析色谱柱分离提纯得到黄色固体，即4,7-二(噻吩-2-基)-5,6-二氨基-N-(2-癸基十四烷基)-异吲哚-1,3-二酮(0.8g，产率60％)。
实施例2：
N-R1-N′-R2-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮的制备，反应式如式II所示：
Figure BDA0001503436670000052
式II中的2-R2-6,7-二氢-1H-茚并[6,7,1-def]异喹啉-1,3,6,7(2H)-四酮(c)的合成参照文献[Herrera H,Echegaray PD,Urdanpilleta M,et al.Chem Commun.2013,49,713]。
以制备N,N-二(2-癸基十四烷基)-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮为例予以说明：在100mL两口瓶中分别加入4,7-二(噻吩-2-基)-5,6-二氨基-N-(2-癸基十四烷基)-异吲哚-1,3-二酮(0.54g，0.8mmol)和2-(2-癸基十四烷基)-6,7-二氢-1H-茚并[6,7,1-def]异喹啉-1,3,6,7(2H)-四酮(0.47g，0.8mmol)，再加入45mL冰乙酸，氮气条件下搅拌回流过夜，再将反应液倒入水中，用二氯甲烷萃取，用无水硫酸镁干燥有机相，过滤，旋干有机相，再用硅胶层析色谱柱分离提纯，得到红色固体N,N-二(2-癸基十四烷基)-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮(0.83g，产率84％)。
1HNMR(500MHz,CDCl3)：δ＝8.69(d,2H)，δ＝8.49(d,2H)，δ＝7.77(dd,2H)，δ＝7.65(dd,2H)，δ＝7.32(q,2H)，δ＝4.14(d,2H)，δ＝3.60(d,2H)，δ＝2.01(m,1H)，δ＝1.93(m,1H)，δ＝1.22-1.42(m,80H)，δ＝0.83-0.88(m,12H)。
实施例3：
N-R1-N′-R2-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1，3(2H)-二酮的制备，反应式如式III所示：
Figure BDA0001503436670000061
以制备N,N-二(2-癸基十四烷基)-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮为例予以说明：在100mL两口瓶中加入N,N-二(2-癸基十四烷基)-7,10-二(噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮(0.86g，0.7mmol)，再加入30mL氯仿和10mL冰乙酸搅拌均匀，再在冰浴条件下加入NBS(0.30g，1.68mmol)，常温反应24h，将反应液倒入水中，用二氯甲烷萃取，无水硫酸镁干燥有机相，过滤，旋干有机相，再用硅胶层析色谱柱分离提纯，得到深红色固体N,N-二(2-癸基十四烷基)-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮(0.73g，产率75％)。
1HNMR(500MHz,CDCl3)：δ＝8.71(d,2H)，δ＝8.52(d,2H)，δ＝7.51(d,2H)，δ＝7.27(d,2H)，δ＝4.14(d,2H)，δ＝3.61(d,2H)，δ＝2.01(m,1H)，δ＝1.92(m,1H)，δ＝1.22-1.43(m,80H)，δ＝0.83-0.87(m,12H)。
13C NMR(126MHz,CDCl3)：δ＝165.92,163.46,154.60,142.09,135.72,135.38,133.36,132.68,132.57,132.22,129.31,128.16,125.33,125.24,124.55,118.19,44.90,43.28,36.85,31.92,31.75,31.62,30.04,29.69,29.66,29.61,29.36,26.53,26.32,22.69,14.12。
实施例4：
含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物P1的合成。
合成路线如下：
Figure BDA0001503436670000071
将单体N,N-二(2-癸基十四烷基)-7,10-二(5-溴-噻吩-2-基)-1H-吡啶并[3',4',5',5,6]苊并[1,2-b]喹喔啉-8,9-二元羧酸酰亚胺-1,3(2H)-二酮(0.208g，0.15mmol)、3,4-二氟-2,5-二三甲基锡噻吩(0.067g，0.15mmol)和四合三苯基膦钯(7mg)加入到25mL两口瓶中，然后加入6mL氯苯将其充分溶解，充入氮气排气泡20分钟，升温至110℃，反应48小时，然后冷却至室温，将反应液滴入200mL甲醇中沉淀出聚合物，将聚合物放入索氏抽提器中先后用甲醇、丙酮、正己烷各抽提24h，洗涤掉小分子和催化剂，然后用氯仿溶解剩余聚合物，滴入甲醇中重新析出来，最后用布氏漏斗收集聚合物，得到黑色聚合物160mg，产率约为80％。
含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物P1的紫外-可见吸收光谱如图1所示，热失重曲线如图2所示(5％失重的热分解温度为430℃)。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (2)

1.一种含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物，其特征在于：结构通式为：
Figure FDA0002303963910000011
其中，n为1～10000的自然数。
2.权利要求1所述的含苊并[1,2-b]喹喔啉二酰亚胺的共轭聚合物作为活性层电子受体或电子给体材料在有机太阳能电池中的应用。
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